Substituted sulfonylaminomethylbenzoic acid (derivatives) and their preparation

ABSTRACT

The present invention relates to a compound of the formula (I)                    
     The compound according to the invention is suitable for the preparation of herbicidal active substances such as sulfonylureas.

The invention relates to the technical field of the intermediates forthe preparation of active substances, in particular herbicidally activesulfonylureas.

It is known that aromatic amines can be reacted to give sulfonic acidderivatives such as sulfochlorides and further to give sulfonamideswhich, in turn, can be employed for the preparation of herbicidallyactive sulfonylureas (Meerwein et al., Chem. Berichte 90, 841-852 (1957)and EP-A-574418).

A substituted anthranilic acid is known from J. Med. Chem. 1986, Vol.29, No. 4, page 585 as intermediate for the preparation of certainanhydrides which are suitable for inactivating trypsin-like enzymes.

It was an object to provide novel chemical compounds which are suitablefor the preparation of herbicidally active sulfonylureas. Surprisingly,this object is achieved by compounds of the formula (I)

in which

R¹ is H, (C₁-C₈)alkyl, (C₃-C₈)alkenyl or (C₃-C₈)alkynyl, where the last3 radicals are unsubstituted or substituted, for example by one or moreradicals selected from the group consisting of halogen, (C₁-C₄)alkoxy,(C₁-C₄)alkylthio, [(C₁-C₄)alkyl]carbonyl or [(C₁-C₄)alkoxy]carbonyl,

R², R³ independently of one another are H or acyl, preferably H,

R⁴, R⁵ are H,

R⁶ is H or (C₁-C₈)alkyl which is unsubstituted or substituted, forexample by one or more radicals selected from the group consisting ofhalogen, (C₁-C₄)alkoxy, (C₁-C₄)alkylthio, (C₁-C₄)alkylsulfinyl,(C₁-C₄)alkylsulfonyl, [(C₁-C₄)alkyl]carbonyl or CN, preferably H,

R⁷ is (C₁-C₈)alkyl, (C₃-C₈)alkenyl or (C₃-C₈)alkynyl which areunsubstituted or substituted, for example by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)alkoxy or(C₁-C₄)alkylthio, or R⁷ is (C₆-C₁₄)aryl (for example phenyl) which isunsubstituted or substituted, for example by one or more radicalsselected from the group consisting of halogen, NO₂, CN, (C₁-C₄)alkyl,(C₁-C₄)haloalkyl or (C₁-C₄)alkoxy, or R⁷ is mono- ordi-(C₁-C₈)alkylamino which is unsubstituted or substituted, for exampleby one or more radicals selected from the group consisting of halogen,(C₁-C₄)alkoxy, (C₁-C₄)alkylthio, (C₁-C₄)alkylsulfinyl,(C₁-C₄)alkylsulfonyl, [(C₁-C₄)alkyl]carbonyl, [(C₁-C₄)alkoxy]carbonyl orCN, or

R⁶ and R⁷ together form a chain of the formula —(CH₂)_(m)B_(m) _(¹) —which is unsubstituted or substituted, for example by one or more(C₁-C₄)alkyl radicals, and where m=2, 3 or 4, m¹=0 or 1 and B═CO or SO₂,

R⁸ radicals, are identical or different and are (C₁-C₄)alkyl,(C₁-C₄)alkoxy, [(C₁-C₄)alkyl]carbonyl or [(C₁-C₄)alkoxy]carbonyl whichare unsubstituted or substituted, for example by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)alkoxy,(C₁-C₄)alkylthio, [(C₁-C₄)alkyl]carbonyl or [(C₁-C₄)alkoxy]carbonyl, orR⁸ is halogen or NH₂, and

n is 0, 1, 2 or 3, preferably 0.

Preferred compounds of the formula (I) are those in which

R¹ is H or (C₁-C₄)alkyl, preferably (C₁-C₄)alkyl,

R² and R³ are H,

R⁴ and R⁵ are H,

R⁶ is H,

R⁷ is (C₁-C₄)alkyl, and

n is 0.

Compounds of the formula (I) which are of particular importance arethose in which the group CR⁴R⁵—NR⁶—SO₂—R⁷ is in the para positionrelative to the group —CO—OR¹. If together form a chain of the formula—(CH₂)_(m)B_(m1)— and m¹=1, it is preferable that B is bound to thenitrogen atom which has R⁶ attached to it.

Examples of compounds of the formula (I) are listed in table 1hereinbelow:

TABLE 1 (Ia)

Compound R¹ R⁶ R⁷ 1 Me H Me 2 Me Me Me 3 Me H NHMe 4 Me Me NHMe 5 Me HN(Me)₂ 6 Me Me N(Me)₂ 7 Me —CH₂—CH₂—CH₂— 8 Me —CH₂—CH₂—CH₂—CH₂— 9 Me HPhe 10 Me Me Phe 11 Me H CH₂F 12 Me Me CH₂F 13 Me H CF₃ 14 Me Me CF₃ 15Me H Et 16 Me Me Et 17 Me H nPr 18 Me Me nPr 19 Me H iPr 20 Me Me iPr 21Me H nBu 22 Me Me nBu 23 Me Et Me 24 Me Et Et 25 Me Et NHMe 26 Me EtN(Me)₂ 27 Me Et Phe 28 Me Et CH₂F 29 Me Et CF₃ 30 Me Et nPr 31 Me Et iPr32 Me Et nBu 33 Et H Me 34 Et Me Me 35 Et H NHMe 36 Et Me NHMe 37 Et HN(Me)₂ 38 Et Me N(Me)₂ 39 Et —CH₂—CH₂—CH₂— 40 Et —CH₂—CH₂—CH₂—CH₂— 41 EtH Phe 42 Et Me Phe 43 Et H CH₂F 44 Et Me CH₂F 45 Et H CF₃ 46 Et Me CF₃47 Et H Et 48 Et Me Et 49 Et H nPr 50 Et Me nPr 51 Et H iPr 52 Et Me iPr53 Et H nBu 54 Et Me nBu 55 Et Et Me 56 Et Et Et 57 Et Et NHMe 58 Et EtN(Me)₂ 59 Et Et Phe 60 Et Et CH₂F 61 Et Et CF₃ 62 Et Et nPr 63 Et Et iPr64 Et Et nBu In table 1, Me = methyl, Et = ethyl, nPr = n-propyl, iPr =isopropyl, nBu = n-butyl, Phe = phenyl.

If the term acyl is used in the present description, it denotes theradical of an organic acid which arises formally by eliminating an OHgroup from the organic acid, for example the radical of a carboxylicacid and radicals of acids derived therefrom, such as thiocarboxylicacid, optionally N-substituted iminocarboxylic acids or the radicals ofcarbonic monoesters, optionally N-substituted carbamic acids, sulfonicacids, sulfinic acids, phosphonic acids, phosphinic acids.

An acyl radical is preferably formyl or acyl from the group consistingof CO—R^(x), CS—R^(x), CO—OR^(x), CS—OR^(x), CS—SR^(x), Cr^(x)═NR^(Y),SOR^(Y)or SO₂ ^(Y), where R^(x) and R^(Y) are each a C₁-C₁₀-hydrocarbonradical such as C₁-C₁₀-alkyl or C₆-C₁₀-aryl, each of which isunsubstituted or substituted, for example by one or more substituentsselected from the group consisting of halogen such as F, Cl, Br, I,alkoxy, haloalkoxy, hydroxyl, amino, nitro, cyano or alkylthio, or acylis aminocarbonyl or aminosulfonyl, the two last-mentioned radicals beingunsubstituted, N-monosubstituted or N,N-disubstituted, for example bysubstituents from the group consisting of alkyl or aryl. Acyl is, forexample, formyl, haloalkylcarbonyl, alkylcarbonyl such as(C₁-C₄)alkylcarbonyl, phenylcarbonyl, it being possible for the phenylring to be substituted, or alkyloxycarbonyl, such as (C₁-C₄)alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl,such as (C₁-C₄) alkylsulfonyl, alkylsulfinyl, such asC₁-C₄(alkylsulfinyl), N-alkyl-1-iminoalkyl, such asN—(C₁-C₄)-1-imino-(C₁-C₄)alkyl and other radicals of organic acids.

In formula (I) and the general formulae used hereinbelow, the radicalsalkyl, alkoxy, haloalkyl, haloalkoxy and alkylthio and the correspondingsubstituted radicals can be in each case straight-chain or branched inthe carbon skeleton. Unless specified otherwise, the lower carbonskeletons, for example those having 1 to 4 carbon atoms, are preferredamongst these radicals. Alkyl radicals, also in the composite meaningssuch as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl,n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls such as n-hexyl,i-hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyls, 1-methylhexyland 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaningsof the possible unsaturated radicals which correspond to the alkylradicals; for example alkenyl is allyl, 1-methylprop-2-en-1-yl,2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl,1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, forexample, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.

Alkenyl, for example in the form “(C₃-C₈)alkenyl”, is preferably analkenyl radical having 3 to 8 carbon atoms in which the double bond isnot positioned at the carbon atom which is linked to the remainingmoiety of the compound (I) (“yl” position). This also appliesanalogously to alkynyl radicals.

Halogen is, for example, fluorine, chlorine, bromine or iodine.Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl, each ofwhich is partially or fully substituted by halogen, preferably byfluorine, chlorine and/or bromine, in particular by fluorine orchlorine, for example CF₃, CHF₂, CH₂F, CF₃CF₂, CH₂FCHCl₂, CCl₃, CHCl₂,CH₂CH₂Cl; haloalkoxy is, for example, OCF₃, OCHF₂, OCH₂F, CF₃CF₂O,OCH₂CF₃ and OCH₂CH₂Cl; this also applies analogously to haloalkenyloxyand other halogen-substituted radicals.

Substituted radicals such as substituted hydrocarbon radicals, forexample substituted alkyl, alkenyl, alkynyl, aryl, for example phenyl,are, for example, a substituted radical which is derived from theunsubstituted skeleton, the substituents being, for example, one ormore, preferably 1, 2 or 3, radicals selected from the group consistingof halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro,carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl,carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such asacylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl,alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals,also alkyl and haloalkyl, and unsaturated aliphatic radicals whichcorrespond to the abovementioned saturated hydrocarbon-containingradicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy and the like.In the case of radicals with carbon atoms, those having 1 to 4 carbonatoms, in particular 1 or 2 carbon atoms, are preferred. Preferred are,as a rule, substituents selected from the group consisting of halogen,for example fluorine and chlorine, (C₁-C₄)alkyl, preferably methyl orethyl, (C₁-C₄)haloalkyl, preferably trifluoromethyl, (C₁-C₄)alkoxy,preferably methoxy or ethoxy, (C₁-C₄)haloalkoxy, nitro and cyano.Especially preferred in this context are substituents methyl, methoxyand chlorine.

Optionally substituted phenyl or phenoxy is preferably phenyl orphenoxy, each of which is unsubstituted or mono- or polysubstituted,preferably up to trisubstituted, by identical or different radicalsselected from the group consisting of halogen, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkyl, (C₁-C₄)haloalkoxy and nitro, forexample o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl,2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

If substitutions are defined by one or more radicals from among a groupof radicals, this encompasses both the substitution by one or moreidentical radicals and the mono- or polysubstitution by differentradicals.

Subject of the invention are also all stereoisomers which areencompassed by formula (I) and their mixtures. Such compounds of theformula (I) contain one or more asymmetric carbon atoms which are notindicated separately in formula (I). The possible stereoisomers whichare defined by their specific spatial shape, such as enantiomers ordiastereomers, are all encompassed by formula (I) and can be obtainedfrom mixtures of the stereoisomers by customary methods or else bystereoselective reactions in combination with the use ofstereochemically pure starting materials. Formula (I) also encompassestautomers of the compounds stated, inasfar as they are formed by protonmigration and are chemically stable.

The compounds of the formula (I) may form salts in which an acidichydrogen atom is replaced by a suitable cation. These salts are, forexample, metal salts; preferably alkali metal salts or alkaline earthmetal salts, in particular sodium salts and potassium salts, or elseammonium salts or salts of organic amines. Likewise, salt formation canbe effected by an addition reaction of an acid with basic groups, suchas amino. Acids which are suitable for this purpose are strong inorganicand organic acids, for example HCl, HBr, H₂SO₄, HNO₃ or formic acid.

Compounds of the formula (I) are successfully synthesized in very goodyields and purities starting from compounds of the formula (II)mentioned hereinbelow.

Subject of the present invention is thus also a process for thepreparation of compounds of the formula (I) comprising the steps of

1a) reacting a compound of the formula (II)

 by catalytic hydrogenation in the absence of an acid to give a compoundof the formula (III) or by catalytic hydrogenation in the presence of anacid, for example H⁺X⁻, where X⁻ is an equivalent of an acid anion, suchas halogen, for example Cl⁻, Br⁻ or I⁻, or HSO₄ ⁻, ½SO₄ ²⁻, H₂PO₄ ⁻,½HOP₄ ²⁻, ⅓PO₄ ³⁻ or ⁻OCOR (where R=H or (C₁-C₈)alkyl) to give acompound of the formula (IIIa), where X⁻ is an equivalent of an acidanion, such as halide, for example Cl⁻, Br⁻ or I⁻, or HSO₄ ⁻, ½SO₄ ²⁻,H₂PO₄ ⁻, ½HPO₄ ²⁻, ⅓PO₄ ³⁻ or ⁻OCOR (where R=H or (C₁-C₈)alkyl),

 and subsequently

1b) reacting the compound of the formula (III) or (IIIa) with a sulfonicacid derivative to give a compound of the formula (I) where R², R³ andR⁶=H; or

2a) α) reacting a compound of the formula (II)

 by customary reduction methods for nitro compounds to give a compoundof the formula (IV),

 and subsequently

 β) reacting the compound of the formula (IV) either by catalytichydrogenation or by customary reduction methods for nitriles to give acompound of the formula (III) or (IIIa),

 and subsequently

2b) reacting the compound of the formula (III) or (IIIa) with a sulfonicacid derivative to give a compound of the formula (I) where R², R³ andR⁶=H; or

3a) α) reacting a compound of the formula (II)

 by customary reduction methods for nitrites to give a compound of theformula (V) or (Va), where X^({circle around (−)}) is as defined informula (IIIa),

 and subsequently

 β) reacting the compound of the formula (V) or (Va) by customaryreduction methods for nitro compounds or by catalytic hydrogenation togive a compound of the formula (III) or (IIIa),

 and subsequently

3b) reacting the compound of the formula (III) or (IIIa) with a sulfonicacid derivative to give a compound of the formula (I) where R², R³ andR⁶=H; or

4a) α) reacting a compound of the formula (II)

 by customary reduction methods for nitrites to give a compound of theformula (V) or (Va), where X⁻ is as defined in formula (IIIa),

 β) and subsequently reacting the compound of the formula (V) or (Va)with a sulfonic acid derivative to give a compound of the formula (VI),

 and subsequently

4b) reacting the compound of the formula (VI) by customary reductionmethods for nitro compounds or by catalytic hydrogenation to give acompound of the formula (I) where R², R³ and R⁶=H.

The compounds of formulae (III), (IIIa), (V), (Va) and (VI) are noveland also subject of the present invention.

Compounds of the formula (I) where R² and/or R³=acyl can be obtained byacylating compounds of the formula (I) where R² and R³=H with acylatingagents such as carbonyl halides, sulfonyl halides and carbamoyl halides,carboxylic anhydrides, sulfonic anhydrides, haloformic esters orisocyanates, by customary methods (see, for example, L.-F. Tietze, Th.Eicher, Reaktionen und Synthesen im organisch-chemischen Praktikum[Reactions and Syntheses in the Organochemical Laboratory Practical],Thieme Verlag Stuttgart/New York, 1981, pp. 131, 316, 318, 345; R. C.Larock, Comprehensive Organic Transformations (1989), pp. 979, 981).Examples of suitable solvents are aprotic solvents such asdichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene orchlorobenzene, preferably at temperatures of from 0° C. to the boilingpoint of the solvent.

Compounds of the formula (I) where R⁶=unsubstituted or substitutedC₁-C₈-alkyl can be obtained for example by alkylating compounds of theformula (I) where R⁶=H with alkylating agents such as alkyl halides,alkyl sulfates such as dimethyl sulfate or alkyl tosylates by customarymethods. Examples of suitable solvents are acetone and dimethylformamide(cf., for example, R. C. Larock, Comprehensive Organic Transformations(1989), p. 398; L.-F. Tietze, Th. Eicher, Reaktionen und Synthesen imorganisch-chemischen Praktikum, Thieme Verlag Stuttgart/New York, 1981,p. 75; Organikum, Organisch-chemisches Grundpraktikum [Basic LaboraryPractical in Organic Chemistry] VEB, Berlin 1981). The alkylation can becarried out in the presence of bases such as K₂CO₃, NaH or alkoxidessuch as sodium alkoxide. The starting material is preferably compoundsof the formula (I) in which R² and R³ are acyl.

Compounds of the formula (I) where R⁶=unsubstituted or substitutedC₁-C₈-alkyl can also be obtained for example via reductive aminations,for example with aldehydes or ketones in the presence of reducing agentssuch as H₂/catalyst, formic acid, zinc/HCl, sodium borohydride or sodiumcyanoborohydride. An example is the Leuckard-Wallach reaction withformaldehyde and formic acid.

Preferred processes are those in which the nitro and the nitrile groupin compounds of the formula (II) are reduced jointly in one process stepby means of catalytic hydrogenation in accordance with process variant1a) to give compounds of the formula (III) or (IIIa).

The amino compounds of the formulae (III) and (V) which are obtained asintermediates in the process according to the invention can also arisein the form of their salts (IIIa) and (Va) and can be reacted furtherwhen the reaction or work-up is effected in an acidic medium.

The symbols given in formulae (II), (III), (IIIa), (IV), (V), (Va) and(VI) have the same meaning as in formula (I), including the preferredranges mentioned herefor. Preferred compounds of the formulae (II),(III), (IIIa), (IV), (V), (Va) and (VI) are those in which the groups—CN (formulae (II) and (IV)), —CH₂—NH₂ (formulae (III) and (V)),—CH₂—NH₃ ⁺X⁻ (formulae (IIIa) and (Va)) and —CH₂—NR⁶—SO₂—R⁷ (formula(VI)) are in the para position relative to the group —CO—OR¹.

Furthermore, substeps of the process according to the invention are alsosubject of the invention.

The compounds of the formula (II) are known, cf., for example, DE 22 39799 C3 or Journal of the American Chemical Society 99, 6721 (1977).

The catalytic hydrogenation of the compound of the formula (II) byprocess variant 1a), of the compound of the formula (IV) by processvariant 2aβ), of the compound of the formula (V) or (Va) by processvariant 3aβ) or of the compound of the formula (VI) by process variant4b) is successfully carried out by means of customary hydrogenationmethods. Examples of hydrogen sources which can be used are hydrogengas, hydrazine or HN═NH. Particularly suitable hydrogenation catalystsare noble-metal catalysts, for example Pd, Pt, Rh, Ir or Ni or Cocatalysts. The noble metals can be used in elemental form or in the formof oxides or halides. The noble-metal catalysts can be used as desiredwithout or, preferably, with support materials such as active charcoal,kieselguhr, silicates.

The hydrogenation can be carried out both by atmospheric pressure and byapplying a superatmospheric hydrogen pressure, as a rule between 1 and100 bar, preferably 1-50 bar. In general, the suitable temperature is inthe range of from −20 to 150° C., preferably between 0 and 120° C.

Examples of solvents which are suitable for the hydrogenation aresolvents of the groups water, alcohols such as methanol or ethanol,ethers such as diethyl ether, tetrahydrofuran or dioxane, amides such asdimethylformamide or dimethylacetamide, esters such as ethyl acetate,organic carboxylic acids such as formic acid or acetic acid, aromatichydrocarbons such as toluene, xylene and chlorobenzene, or halogenatedaliphatic hydrocarbons such as CH₂Cl₂, it being possible to employ thesolvents in pure form or as mixtures.

The catalytic hydrogenation of the compounds of the formula (II) byprocess variant 1a) or of the compounds of the formula (IV) by processvariant 2aβ) is preferably carried out in the presence of 1-10 molarequivalents of an acid. Solvents which are preferably used are alcoholssuch as methanol or ethanol, or water. Examples of suitable acids areinorganic acids or carboxylic acids. Preferred are acids of the formulaH⁺X⁻ where X⁻ is an equivalent of an acid moiety, such as halogen forexample Cl⁻, Br⁻ or I⁻, or HSO₄ ⁻, ½SO₄ ²⁻, H₂PO₄ ⁻, ½HPO₄ ²⁻, ⅓PO₄ ³⁻or ⁻OCOR (where R=H or (C₁-C₈)alkyl), for example hydrohalic acids suchas hydrochloric acid or hydrobromic acid, or sulfuric acid, phosphoricacid, formic acid or acetic acid. If, for example, the twolast-mentioned acids are used, the acids may also fully assume the roleof the solvent.

The catalytic hydrogenation of the compounds of the formula (IV) canalso be carried out by using 1-10 molar equivalents of ammonia, nickelor cobalt catalysts such as Raney nickel or Raney cobalt preferablybeing employed. Solvents which are preferably used in this context arealcohols such as methanol or ethanol.

The reduction of the nitro group in compounds of the formula (II) byprocess variant 2aα), compounds of the formulae (V) and (Va) by processvariant 3aβ) or compounds of the formula (VI) by process variant 4b) canbe carried out with customary reducing agents for aromatic nitrocompounds. Such reducing agents and reaction conditions are described,for example, in R. C. Larock, Comprehensive Organic Transformations(1989) pp. 411-415, VCH Publishers Inc. and the literature citedtherein. Examples of preferred reducing agents are Fe, Zn, Sn or theirsalts such as FeSO₄ or Sn-II salts such as SnCl₂. Examples of suitablesolvents are organic carboxylic acids, alcohols and/or mineral acids. Ingeneral, the reaction temperature is between 0° C. and the boiling pointof the solvent.

The reduction of the nitrile group in compounds of the formula (IV) byprocess variant 2aβ) and compounds of the formula (II) by processvariant 3aα) and 4aα) can be carried out by customary reducing agentsfor nitrites. Such reducing agents and reaction conditions aredescribed, for example, in R. C. Larock, Comprehensive OrganicTransformation (1989) pp. 437-438, VCH Publishers Inc. and theliterature cited therein. Examples of preferred reducing agents areboron hydride compounds or aluminum hydride compounds such as BH₃/THF,BH₃/DMS and their salts such as NaBH₄. Examples of suitable solvents areethers such as dioxane or tetrahydrofuran. The reaction temperature isgenerally between 0° C. and the boiling point of the solvent. If thereduction product is subsequently worked up in an acid medium, forexample methanol/HCl, the compound of the formula (III) (process variant2aβ) or the compound of the formula (V) (process variants 3aα and 4aα)can be obtained in the form of a salt of the formula (IIIa) or (Va),respectively, which can be reacted further analogously to compound (III)or compound (V), respectively.

The acylation of the compounds of the formula (III) or (IIIa) by processvariant 1b), 2b) or 3b) or of the compounds of the formula (V) or (Va)by process variant 4aβ) with a sulfonic acid derivative can be carriedout under customary conditions for acylation reactions to give thecompounds of the formula (VI) in the case of compounds of the formula(V) or (Va) or to give the compounds of the formula (I) according to theinvention in the case of compounds of the formula (III) or (IIIa).

For example, compounds of the formula (III) or (IIIa), or (V) or (Va),are reacted in suitable solvents with sulfonic acid derivatives in thepresence of bases as acid acceptors to give compounds of the formula (I)or (VI) respectively. Examples of solvents which are suitable for theacylations are solvents from the groups water, alcohols such as methanolor ethanol, halogenated aliphatic hydrocarbons such as CH₂Cl₂, aromatichydrocarbons such as toluene, chlorobenzene or xylene, ethers such asdiethyl ether, tetrahydrofuran or dioxane, ketones such as acetone ormethyl isobutyl ketone, esters such as ethyl acetate, and aproticsolvents such as acetonitrile, dimethylformamide or dimethylacetamide,it being possible for the solvents to be employed in pure form or asmixtures. Preferred are water and mixtures of water and water-solubleorganic solvents from the abovementioned groups.

Bases which are suitable are inorganic or organic bases, for examplecarbonates such as K₂CO₃, Na₂CO₃ or NaHCO₃, alkali metal hydroxides andalkaline earth metal hydroxides such as NaOH, KOH or Ca(OH)₂, or aminessuch as triethylamine. In general, the bases are employed in amounts of1-10 molar equivalents, preferably 1-5 molar equivalents, per compoundof the formula (III) or (V); when compounds of the formula (IIIa) or(Va) are employed, the minimum amount of the base employed is at leasttwo molar equivalents.

Examples of suitable sulfonic acid derivatives are sulfonyl halides suchas fluorides, chlorides, bromides or iodides, and sulfonic anhydrides.Preferred are sulfonic acid derivatives of the formula R⁷—SO₂—Z, whereR⁷ is defined as in formula (I), and Z is a leaving group such ashalogen (for example fluorine, chlorine, bromine or iodine) orO—SO₂—R^(Z), where R^(Z) is as defined for R⁷ in formula (I). Theacylation is carried out for example in such a way that the compounds ofthe formula (III) or (IIIa), or (V) or (Va), are reacted with thesulfonic acid derivatives in suitable solvents in the presence of asuitable base, in general at temperatures of from −20 to 100° C.Preferred are temperatures of from −10 to 50° C. The amounts of sulfonicacid derivatives are generally 1-10 molar equivalents, preferably 1-5molar equivalents, per compound of the formula (III) or (IIIa), or (V)or (Va).

In addition to compounds of the formula (I) and their preparation, thepresent invention also relates to their further reaction to givecompounds of the formulae (VII) and (VIII). To do this, compounds of theformula (I) where R² and/or R³=acyl must first be converted by customarymethods into compounds of the formula (I) where R²═R³═H, and these arethen further reacted to give compounds of the formulae (VII) and (VIII).The symbols used in formulae (VII) and (VIII) have the same meanings asstated for formula (I), including the preferred ranges stated herefor,and Y in formula (VII) is halogen such as fluorine, chlorine, bromine oriodine. Preferred compounds of the formulae (VII) and (VIII) are thosein which the group —CH₂—NR⁶—SO₂—R⁷ is in the para position relative tothe group —CO—OR¹.

As is described in (EP-A-723 534), compounds of the formulae (VII) and(VIII) are suitable precursors for the preparation of potent herbicidalsulfonylureas, the preparation of the compounds of the formulae (VII)and (VIII) being especially efficient in the present process accordingto the invention and the compounds of the formulae (VII) and (VIII)being obtained in very good yields and purities.

Methods for the conversion 6) of anilines into sulfonyl halides areknown (see, for example, H. Meerwein et al., Chem. Berichte 90, 841-852(1957)). Surprisingly, compounds of the formula (I) where R², R³═H aresuccessfully reacted to give compounds of the formula (VII) on the basisof procedures described in the literature. Thus, compounds of theformula (I) where R², R³═H can be diazotized under suitable conditionsand subsequently coupled with suitable SO₂ sources, such as SO₂ gas,Na₂S₂O₅ or NaHSO₃ in the presence of acids such as carboxylic acids, forexample acetic acid, or inorganic acids, for example hydrohalic acids HYsuch as HCl or HBr, and catalysts, for example copper catalysts based onCu(I) and/or Cu(II) salts to give sulfonyl halides of the formula (VII).

The diazotization can be carried out with suitable diazotizing agentssuch as NaNO₂ in the presence of acids such as inorganic acids,preferably hydrohalic acids HY, such as HCl or HBr. The solvent used ispreferably a water/acid mixture, in particular a mixture ofwater/carboxylic acid (for example acetic acid) or water/mineral acid(for example hydrohalic acid HY such as HCl or HBr). In general, thereaction temperature is −20 to 50° C., preferably −10 to 20° C.

The following are examples which can be used as solvents for thesubsequent coupling reaction: water, carboxylic acids such as aceticacid, carboxylic esters such as ethyl acetate, ethers such as diethylether, tetrahydrofuran or dioxane, halogenated aliphatic hydrocarbonssuch as CH₂Cl₂ or dichloroethane, aromatic hydrocarbons such as toluene,chlorobenzene or xylene, or ketones such as acetone or methyl isobutylketone. Moreover, the reaction mixture contains acids, for examplecarboxylic acids such as acetic acid or mineral acids such as hydrohalicacids HY, for example HCl or HBr, which are either still present fromthe diazotization reaction and/or are added when the coupling reactionis carried out. Examples of SO₂ sources which can be used are, forexample, SO₂ gas (1-10 equivalents), Na₂S₂O₅ (1-10 equivalents) orNaHSO₃ (1-10 equivalents), in the presence of catalysts, for examplecopper catalysts such as CuCl (1-20 mol %), CuCl₂ (1-20 mol %), CuBr(1-20 mol %) or CuBr₂ (1-20 mol %).

Starting from sulfonyl halides of the formula (VII) the aminolysis 7)which yields sulfonic amides of the formula (VIII) is, surprisingly,successfully carried out with high efficiency and in high yields byreacting compounds of the formula (VII) for example in suitable solventswith ammonia.

The aminolysis can be carried out with suitable reagents, for example2-10 molar equivalents of aqueous ammonia solution or NH₃ gas in thepresence of a solvent, for example ketones such as acetone or methylisobutyl ketone, halogenated aliphatic hydrocarbons such as CH₂Cl₂,aromatic hydrocarbons such as xylene, toluene or chlorobenzene, etherssuch as diethyl ether, tetrahydrofuran or dioxane, esters such as ethylacetate, aprotic solvents such as dimethylformamide, dimethylacetamideor acetonitrile, or mixtures of these solvents. In general, the reactiontemperature is from −10 to 100° C., preferably −10 to 40° C., especiallypreferably −10 to 20° C.

The compounds of the formulae (VII) and (VIII) can subsequently bereacted in various ways to give sulfonylureas, preferably sulfonylureasof the formula (XIII) and/or their salts, for example by

8) reacting a sulfonyl halide of the formula (VII) with a cyanate MOCN,in which M is an ammonium ion or an alkali metal ion such as Li, Na orK, and with an amino heterocycle of the formula (XII) in the presence ofa base to give the sulfonylurea; or

9) reacting a compound of the formula (VIII) with a heterocycliccarbamate of the formula (IX), in which Ph is unsubstituted orsubstituted phenyl to give the sulfonylurea; or

10) a) first reacting an amino heterocycle of the formula (XII) in thepresence of a base such as trialkylamine, for example triethylamine,with phosgene to give a heterocyclyl isocyanate of the formula (X), andb) reacting the heterocyclyl isocyanate formed, of the formula (X), witha phenylsulfonamide of the formula (VIII) to give the sulfonylurea; or

11) a) reacting a compound of the formula (VIII) with an alkylisocyanate, for example RNCO, in which R=C₁-C₁₀-alkyl and with phosgeneto give a sulfonyl isocyanate of the formula (XI), and b) reacting thesulfonyl isocyanate formed, of the formula (XI), with an aminoheterocycle of the formula (XII) to give the sulfonylurea; or

12) a) reacting a compound of the formula (VIII) with a carbonic acidderivative such as R—CO—OPh, in which Ph=unsubstituted or substitutedphenyl and R=halogen or unsubstituted or substituted phenoxy to give aphenylsulfonyl carbamate of the formula (XIV), and b) reacting thephenylsulfonyl carbamate formed, of the formula (XIV), in whichPh=unsubstituted or substituted phenyl, with an amino heterocycle of theformula (XII) to give the sulfonylurea.

The symbols used in formulae (IX), (X), (XI), (XII), (XIII) and (XIV)have the same meaning as stated in formula (I), including the preferredranges stated herefor; in addition, the following meanings are also usedtherein:

R^(x), R^(y) independently of one another are a hydrogen atom, halogen,(C₁-C₄)alkyl, (C₁-C₄)alkoxy, (C₁-C₄)alkylthio, where each of thelast-mentioned 3 radicals is unsubstituted or substituted by one or moreradicals selected from the group consisting of halogen, (C₁-C₄)alkoxyand (C₁-C₄)alkylthio, or are mono- or di[(C₁-C₄)alkyl]amino,(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (C₃-C₆)alkenyloxy or (C₃-C₆)alkynyloxy,

X is CH or N, and

Y is halogen such as fluorine, chlorine, bromine or iodine, preferablychlorine.

Preferred compounds of the formulae (XI), (XIII) and (XIV) are those inwhich the group —CH₂—NR⁶—SO₂—R⁷ is in the para position relative to thegroup —COOR¹.

Sulfonylureas such as the compounds of the formula (XIII) can form saltsin which the hydrogen of the —SO₂—NH— group is replaced by anagriculturally suitable cation. Examples of these salts are metal salts,in particular alkali metal salts or alkaline earth metal salts, inparticular sodium salts and potassium salts, or else ammonium salts orsalts with organic amines. Likewise, salt formation can be effected byan addition reaction of an acid with basic groups, such as, for example,amino and alkylamino. Acids which are suitable for this purpose arestrong inorganic and organic acids, for example HCl, HBr, H₂SO₄ or HNO₃.If the present description mentions sulfonylureas such as the compoundsof the formula (XIII), this is also to be understood as including theirsalts in each case.

In process variant 8), the reaction of the sulfonyl halides (VII) iscarried out with amino heterocycles of the formula (XII) and cyanatesMOCN preferably with base catalysis in inert aprotic organic solventssuch as ethyl acetate, tetrahydrofuran, toluene or acetonitrile between0° C. and the boiling point of the solvent. Examples of suitable basesare organic amine bases, in particular pyridines such as pyridine or3-methylpyridine.

In process variant 9), the reaction of the compounds of the formulae(VIII) and (IX) is carried out preferably with base catalysis in aninert organic solvent such as dichloromethane, acetonitrile, dioxane,tetrahydrofuran or ethyl acetate at between 0° C. and the boiling pointof the solvent. Examples of bases which are used are K₂CO₃ or organicamine bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

In process variant 10), the reaction of the compound of the formula(XII) is carried out with phosgene to give heterocyclyl isocyanates ofthe formula (X), for example in inert organic solvents such as ethylacetate, dioxane or aromatic solvents such as chlorobenzene, ifappropriate with addition of an organic amine base such astriethylamine, in general between 0° C. and the boiling point of thesolvent. The subsequent reaction of the compound of the formula (X) withthe compound of the formula (VIII) is carried out for example in inertsolvents such as ethyl acetate, dioxane or aromatic solvents such aschlorobenzene, preferably in the presence of bases such as K₂CO₃ ortrialkylamines such as triethylamine or tributylamine, in general attemperatures of from −20° C. to the boiling point of the solvent (cf.for example, EP-A-232 067 or EP-A-166516).

In process variant 11), the reaction of the compound of the formula(VIII) is carried out with an alkyl isocyanate and phosgene to givephenylsulfonyl isocyanates of the formula (XI), for example in inertsolvents such as dichloromethane, acetonitrile, dioxane,tetrahydrofuran, toluene or chlorobenzene, in general at temperatures offrom 20° C. to the boiling point of the solvent. The subsequent reactionof the compound of the formula (XI) with amino heterocycles of theformula (XII) is carried out for example in inert solvents such asdichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene orchlorobenzene, in general at temperatures of from 0° C. to the boilingpoint of the solvent (cf. for example U.S. Pat. No. 4,481,029).

In process variant 12), the reaction of the compound of the formula(VIII) with a carbonic acid derivative, for example diphenyl carbonateor phenyl chloroformate, to give a phenylsulfonyl carbamate of theformula (XIV) is carried out for example in inert solvents such asxylene, dichloromethane, acetonitrile, dioxane, tetrahydrofuran, tolueneor chlorobenzene, preferably in the presence of a base such as K₂CO₃ ororganic amine bases such as triethylamine, preferably at temperatures offrom 20° C. to the boiling point of the solvent (cf., for example, U.S.Pat. No. 4,684,393 and U.S. Pat. No. 4,743,290). The subsequent reactionof the compound of the formula (XIV) with amino heterocycles of theformula (XII) is carried out for example in inert solvents such asxylene, dichloromethane, acetonitrile, dioxane, tetrahydrofuran, tolueneor chlorobenzene, in general at temperatures of between 20° C. and theboiling point of the solvent.

The compounds of the formula (I) according to the invention thus makepossible an efficient preparation of herbicidal sulfonylureas and otheractive substances.

EXAMPLES Example 1

a) 3-Amino-4-methoxycarbonylbenzylammonium chloride

After addition of 365 ml of concentrated hydrochloric acid (4.37 mol)and 9 g of PtO₂, a suspension of 900 g (4.37 mol) of methyl4-cyano-2-nitrobenzoate in 13.5 l of methanol is first hydrogenated atroom temperature at a hydrogen pressure of 1 bar. After the hydrogenuptake has subsided, the pressure is increased to 17 bar, andhydorgenation is continued until the hydrogen uptake is complete. Forwork-up, the pressure is released to atmospheric pressure, the catalystis removed by filtration through silica gel and the filtrate isconcentrated completely in vacuo. Digestion of the residue with ethylacetate yields 3-amino-4-methoxycarbonylbenzylammonium chloride, yield757 g (80%), melting point 185-190° C. (decomp.).

b) Methyl 2-amino-4-methanesulfonylaminomethylbenzoate

3 g of 3-amino4-methoxycarbonylbenzylammonium chloride (18.8 mmol) aredissolved in 50 ml of dimethylacetamide, triethylamine (2.8 g, 27.7mmol) is added, and the mixture is subsequently reacted at 0-10° C. witha solution of methanesulfonyl chloride (1.6 g, 13.8 mmol) in 20 ml ofdimethylacetamide. After 1 h, the solvent is removed in vacuo and theresidue is worked up by extraction with water/dichloromethane. Thecombined organic extracts are washed with water and dried (Na₂SO₄) andthen evaporated on a rotary evaporator. The residue obtained iscrystallized from water, whereupon 3 g (84%) of methyl2-amino-4-methanesulfonylaminomethylbenzoate of melting point 120-121°C. are obtained.

c) Methyl 2-chlorosulfonyl-4-methanesulfonylaminomethylbenzoate

After addition of 5 ml of glacial acetic acid, a solution of 3 g (11.6mmol) of methyl 2-amino-4-methanesulfonylaminomethylbenzoate in 20 ml ofconcentrated hydrochloric acid is treated at 0-5° C. over 0.5 h with anaqueous NaNO₂ solution (0.81 g, 11.7 mmol, 10 ml of water), and stirringis continued for 0.5 h at 5° C. In parallel, 0.34 g (3.5 mmol) of CuClis suspended in 30 ml of glacial acetic acid which had previously beensaturated with SO₂ gas, and the mixture was subsequently treated with 30ml of toluene. The diazonium salt solution which had been preparedbeforehand is added dropwise to this mixture at 35° C. over 0.5 h, withthe evolution of gas starting spontaneously. After 1 hour, the mixtureis treated with water, the phases are separated and the aqueous phase isreextracted with dichloromethane. The combined organic phases arewashed, dried (Na₂SO₄) and concentrated in vacuo. Extracting the residueby stirring with toluene yields 2.5 g (63%) of methyl2-chlorosulfonyl-4-methanesulfonylaminomethylbenzoate of melting point93-94° C.

d) Methyl 2-sulfamoyl-4-methanesulfonylaminomethylbenzoate

A solution of 11 g (32 mmol) of methyl2-chlorosulfonyl-4-methanesulfonylaminomethylbenzoate in 200 ml of THFis treated at 0° C. with 1.1 g (64 mmol) of NH₃ gas. For work-up, themixture is concentrated in vacuo. Extracting the residue by stirringwith water and then filtration and drying in vacuo give 8.3 g (80%) ofmethyl 2-sulfamoyl-4-methanesulfonylaminomethylbenzoate of melting point185-187° C.

e) Methyl2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methanesulfonaminomethylbenzoate

87.15 g (0.2677 mol) of methyl2-sulfamoyl-4-methanesulfonylaminomethylbenzoate and 74.42 g (0.2677mol) of N-(4,6-dimethoxypyrimidin-2-yl)phenylcarbamate are suspended in600 ml of acetonitrile with ice-cooling at 5° C., and the mixture istreated with 40.4 ml (0.2677 mol) of 1,8-diazabicyclo[5.4.0]undec-7-enein the course of 0.5 hours. After 2 hours at room temperature, approx. ⅔of the solvent is removed in vacuo and the residue is stirred vigorouslywith 600 ml of 2N HCl and 400 ml of diisopropyl ether. The product whichhas precipitated is filtered off with suction, washed in succession withwater and diisopropyl ether (in each case twice) and dried in vacuo.This gives 125 g of methyl2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methanesulfonaminomethylbenzoate(92%) of melting point 191-193° C. (decomp.).

Example 2

3-Amino-4-methoxycarbonylbenzylammonium chloride

18.5 g (0.09 mol) of methyl 4-cyano-2-nitrobenzoate and 0.93 g ofpalladium hydroxide (20% on charcoal) are suspended in a mixture of 8 mlof concentrated hydrochloric acid (30% strength) and 315 ml of water ina Hastelloy stirred autoclave. Then, the mixture is hydrogenated at ahydrogen pressure of 17 bar until the hydrogen uptake is complete. Afterthe pressure in the autoclave has been released and the catalystfiltered off, the filtrate is evaporated completely. This gives 19.5 g(97% strength) of 3-amino-4-methoxycarbonylbenzylammonium chloride ofmelting point 200-205° C.

Example 3

3-Amino-4-methoxycarbonylbenzylammonium chloride

In a stainless steel autoclave, 8.0 g of palladium hydroxide (20% oncharcoal) and 100 ml of acetic acid are made inert with N₂. Then, ahydrogen pressure of 17 bar is applied. A solution of 300 g (1.455 mol)of methyl 2-nitro-4-cyanobenzoate in 2.6 l of acetic acid is thenmetered into the vigorously stirred mixture over 3 hours at +20° C. withcooling, using a metering pump. The H₂ pressure is kept at 17 bar. Thepressure in the autoclave is released and the contents are made inertwith N₂. The catalyst is filtered off and the filtrates are evaporated.Yield (acetate of the product): 91% of theory in the form of viscousresidue. By dissolving the residue in toluene and passing in HCl gas (1equivalent) at 0 to +10° C., a quantitative precipitate of3-amino-4-methoxycarbonylbenzylammonium chloride is obtained, which isfiltered off in the form of white crystals and dried (yield 91%, meltingpoint 204-206° C.).

Example 4

a) 3-Nitro-4-methoxycarbonylbenzylammonium chloride

700 ml of a 1 M BH₃ solution in THF (0.7 mol) are metered in the courseof one hour at 40-50° C. into a solution of 144 g (0.7 mol) of methyl4-cyano-2-nitrobenzoate in 250 ml of THF and the mixture is subsequentlyrefluxed for a further 1.5 hours. The reaction mixture is then treatedwith 600 ml of methanol saturated with hydrogen chloride gas, withice-cooling, and refluxed for one hour. The mixture is concentratedcompletely under atmospheric pressure and reevaporated with 700 ml ofmethanol. The residue which remains is stirred with 500 ml of ethylacetate and filtered, and the product is dried. This gives 115 g (67%)of 3-nitro-4-methoxycarbonylbenzyl-ammonium chloride of melting point247-248° C.

b) Methyl 4-methanesulfonylaminomethyl-2-nitrobenzoate

9.4 ml (0.244 mol) of methanesulfonyl chloride are metered over 30minutes with ice-cooling to a solution of 30.1 g (0.122 mol) of3-nitro-4-methoxycarbonyl-benzylammonium chloride and 34 ml (0.244 mol)of triethylamine in 300 ml of dichloromethane, and stirring of themixture is continued for one hour. For work-up, the reaction mixture istreated with ice water, the phases are separated, and the aqueous phaseis reextracted twice more with dichloromethane. After drying (Na₂SO₄),filtration and concentration, 31.3 g (89%) of methyl4-methanesulfonylaminomethyl-2-nitrobenzoate remain as a syrupy oil.

c) Methyl 2-amino-4-methanesulfonylaminomethylbenzoate

13.25 g (46 mmol) of methyl 4-methanesulfonylaminomethyl-2-nitrobenzoateare dissolved in 200 ml of methanol. After addition of 1.4 ml (46 mmol)of concentrated hydrochloric acid and 1 g of Pd catalyst (10% on activecharcoal), the mixture is hydrogenated with hydrogen under atmosphericpressure until the hydrogen uptake is complete. The mixture is removedfrom the catalyst by filtration and the filtrate is concentratedcompletely. Crystallization of the residue from water yields 10.4 g(88%) of methyl 2-amino-4-methanesulfonylaminomethylbenzoate of meltingpoint 121-122° C.

We claim:
 1. A compound of the formula (I),

in which R¹ is H, (C₁-C₈)alkyl, (C₃-C₈)alkenyl or (C₃-C₈)alkynyl, wherethe last 3 radicals are unsubstituted or substituted, R², R³independently of one another are H or acyl, R⁴, R⁵ are H, R⁶ is H or(C₁-C₈)alkyl which is unsubstituted or substituted, R⁷ is (C₁-C₈)alkyl,(C₃-C₈)alkenyl, (C₃-C₈)alkynyl, (C₆-C₁₄)aryl or mono- or di(C₁-C₈)alkylamino which are unsubstituted or substituted, or R⁶ and R⁷together form a chain of the formula —(CH₂)_(m),B_(m1)— which isunsubstituted or substituted, and where m=2, 3 or 4, m¹=0 or 1 and B=COor SO₂, R⁸ radicals are identical or different and are (C₁-C₄)alkyl,(C₁-C₄)alkoxy, [(C₁-C₄)alkyl]carbonyl or [(C₁-C₄)alkoxy]carbonyl whichare unsubstituted or substituted, or R⁸ is halogen, NO₂ or CN, and n is0, 1, 2 or 3, wherein, unless otherwise identified, the substituents arehalogen, (C₁-C₈)alkoxy, (C₁-C₈)haloalkoxy, (C₁-C₈)alkylthio, hydroxyl,amino, nitro, carboxyl, cyano, azido (C₁-C₈)alkoxycarbonyl,(C₁-C₈)alkylcarbonyl, formyl, carbamoyl, mono- and di-(C₁-C₈)alkylaminocarbonyl, acylamino, mono- and di-(C₁-C₈) alkylamino,(C₁-C₈)alkylsulfinyl, (C₁-C₈)haloalkylsulfinyl, (C₁-C₈)alkylsulfonyl,halo(C₁-C₈)alkylsulfonyl, (C₁-C₈)cycloalkyl, (C₁-C₈) cycloalkenyl,wherein the cycloalkyl and cycloalkyl radicals are optionallysubstituted by (C₁-C₈)alkyl and halo(C₁-C₈)alkyl, (C₁-C₈)alkenyl,(C₁-C₈)alkynyl, (C₁-C₈)alkenyloxy or (C₁-C₈)alkynyloxy.
 2. A compound ofthe formula (I) as claimed in claim 1, where R¹ is H or (C₁-C₄)alkyl,preferably (C₁-C₄)alkyl, R², R³ are H, R⁴, R⁵ are H, R⁶ is H, R⁷ is(C₁-C₄)alkyl, and n is
 0. 3. A compound of the formula (I) as claimed inclaim 1, in which the group —CR⁴R⁵—NR⁶—SO₂—R⁷ is in the para positionrelative to the group —CO—OR¹.
 4. A process for the preparation of acompound of the formula (I) as claimed in of claim 1, comprising thesteps of: 1a) reacting a compound of the formula (II)

by catalytic hydrogenation in the absence of an acid to give a compoundof the formula (III) or by catalytic hydrogenation in the presence of anacid H⁺X⁻, where X⁻ is an equivalent of an acid anion, to give acompound of the formula (IIIa), where X⁻ is an equivalent of an acidanion,

and subsequently 1b) reacting the compound of the formula (III) or(IIIa) with a sulfonic acid derivative to give a compound of the formula(I) where R², R³ and R⁶=H; or 2a) α) reacting a compound of the formula(II)

with a reagent that reduces a nitro group to an amine to give a compoundof the formula (IV),

and subsequently (β) reacting the compound of the formula (IV) either bycatalytic hydrogenation or with a reagent that reduces a nitrile to anamine to give a compound of the formula (III) or (IIIa), andsubsequently 2b) reacting the compound of the formula (III) or (IIIa)with a sulfonic acid derivative to give a compound of the formula (I)where R², R³ and R⁶=H; or 3a) α) reacting a compound of the formula (II)

with a reagent that reduces a nitrile to an amine to give a compound ofthe formula (V) or (Va), where X⁻ is as defined in formula (IIIa),

and subsequently (β) reacting the compound of the formula (V) or (Va)with a reagent that reduces a nitro group to an amine or by catalytichydrogenation to give a compound of the formula (III) or (IIIa), andsubsequently 3b) reacting the compound of the formula (III) or (IIIa)with a sulfonic acid derivative to give a compound of the formula (I)where R², R³ and R⁶=H; or 4a) α) reacting a compound of the formula (II)

with a reagent that reduces a nitrile to an amine to give a compound ofthe formula (V) or (Va), where X⁻ is as defined in formula (IIIa),

(β) and subsequently reacting the compound of the formula (V) or (Va)with a sulfonic acid derivative to give a compound of the formula (VI),

and subsequently 4b) reacting the compound of the formula (VI) with areagent that reduces a nitro group to an amine or by catalytichydrogenation to give a compound of the formula (I) where R², R³ andR⁶=H, where R¹, R⁷, R⁸ and n in formulae (II), (III), (IIIa), (IV), (V),(Va) and (VI) are as defined in formula (I) in claim 1; and optionallysubsequently 5) reacting the compound of the formula (I) obtained in oneof steps 1)-4) with an alkylating agent or by reductive amination togive a compound of the formula (I) where R⁶=unsubstituted or substitutedC₁-C₈-alkyl, or with an acylating agent to give a compound of theformula (I) where R² and/or R³=acyl. xxxxxxx
 5. A process for thepreparation of a compound of the formula (XIII), in which R¹, R⁶, R⁷, R⁸and n are as defined in formula (I) in claim 1, R^(x), R^(y)independently of one another are a hydrogen atom, halogen, (C₁-C₄)alkyl,(C₁-C₄)alkoxy, (C₁-C₄)alkylthio, where each of the last-mentioned 3radicals is unsubstituted or substituted by one or more radicalsselected from the group consisting of halogen, (C₁-C₄)alkoxy and(C₁-C₄)alkylthio, or are mono- or di[(C₁-C₄)alkyl]amino, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, (C₃-C₆)alkenyloxy or (C₃-C₆)alkynyloxy, and X is CH orN,

comprising the steps of A) preparing a compound of the formula (I) asdefined in claim 1, where R² and R³=H, by 1a) reacting a compound of theformula (II)

by catalytic hydrogenation in the absence of an acid to give a compoundof the formula (III) or by catalytic hydrogenation in the presence of anacid H⁺X⁻, where X⁻ is an equivalent of an acid anion, to give acompound of the formula (IIIa), where X⁻ is an equivalent of an acidanion,

and subsequently 1b) reacting the compound of the formula (III) or(IIIa) with a sulfonic acid derivative to give a compound of the formula(I) where R², R³, and R⁶=H; or 2a) α) reacting a compound of the formula(II)

with a reagent that reduces a nitro group to an amine to give a compoundof the formula (IV),

and subsequently β) reacting the compound of the formula (IV) either bycatalytic hydrogenation or with a reagent that reduces a nitrile to anamine to give a compound of the formula (III) or (IIIa), andsubsequently 2b) reacting the compound of the formula (III) or (IIIa)with a sulfonic acid derivative to give a compound of the formula (I)where R², R³ and R⁶=H; or 3a) α) reacting a compound of the formula (II)

with a reagent that reduces a nitrile to an amine to give a compound ofthe formula (V) or (Va), where X⁻ is as defined in formula (IIIa),

and subsequently β) reacting the compound of the formula (V) or (Va)with a reagent that reduces a nitro compound to an amine or by catalytichydrogenation to give a compound of the formula (III) or (IIIa), andsubsequently 3b) reacting the compound of the formula (III) or (IIIa)with a sulfonic acid derivative to give a compound of the formula (I)where R², R³ and R⁶=H; or 4a) α) reacting a compound of the formula (II)

with a reagent that reduces a nitro compound to an amine to give acompound of the formula (V) or (Va), where X⁻ is as defined in formula(IIIa),

β) and subsequently reacting the compound of the formula (V) or (Va)with a sulfonic acid derivative to give a compound of the formula (VI),

and subsequently 4b) reacting the compound of the formula (VI) with areagent that reduces a nitro compound to an amine or by catalytichydrogenation to give a compound of the formula (I) where R², R³ andR⁶=H; where R¹, R⁷, R⁸ and n in formulae (II), (III), (IIIa), (IV), (V),(Va) and (VI) are as defined in formula (I) in claim 1; and optionallysubsequently 5) reacting the compound of the formula (1) which has beenobtained in one of steps A1)-A4) with an alkylating agent or byreductive amination to give a compound of the formula (1) whereR⁶=unsubstituted or substituted C₁-C₈alkyl; and subsequently B)preparing a compound of the formula (VII) by 6) reacting the compound ofthe formula (I) which has been obtained in step A) to give a compound ofthe formula (VII),

the compound of the formula (1) being reacted in the presence of an acidwith a diazotizing agent and subsequently with an SO₂ source in thepresence of a copper catalyst and an acid, where R¹, R⁶, R⁷, R⁸ and n informula (VII) are as defined in formula (1) in claim 1 and Y=halogen;and subsequently C) preparing the compound of the formula (XIII) by C1)reacting the compound of the formula (VII) which has been obtained instep B6) with an amine of the formula (XII) in the presence of MOCN,wherein M is an ammonium ion or an alkali metal ion, to give a compoundof the formula (XIII); or

C2.1) preparing a compound of the formula (VIII) by 7) reacting thecompound of the formula (VII) which has been obtained in step B6) togive a compound of the formula (VIII),

the compound of the formula (VIII) being subjected to aminolysis withammonia in a suitable solvent, where R¹, R⁶, R⁷, R⁸ and n in formula(VIII) are as defined in formula (1) in claim 1; and subsequently C2.2)preparing the compound of the formula (XIII) by 9) reacting the compoundof the formula (VIII) with a compound of the formula (IX) to give thecompound of the formula (XIII); or

10) reacting the compound of the formula (VIII) with an isocyanate ofthe formula (X) to give the compound of the formula (XIII); or

11) reacting the compound of the formula (VIII) with an alkyl isocyanateand phosgene to give a compound of the formula (XI),

which is subsequently reacted with an amine of the formula (XIII) togive the compound of the formula (XIII); or

12) reacting the compound of the formula (VIII) with a carbonic acidderivative R—CO—OPh, in which Ph=unsubstituted or substituted phenyl andR=halogen or unsubstituted or substituted phenoxy to give a compound ofthe formula (XIV),

which is subsequently reacted with an amine of the formula (XII) to givethe compound of the formula (XIII);

where R¹, R⁷, R⁸, and n in formulae (XI) and (XIV) are as defined informula (1) in claim 1, R^(x), R^(y) and X in formulae (IX), (X) and(XII) are as defined in formula (XIII) of the present claim and Ph informulae (IX) and (XIV) is unsubstituted or substituted phenyl, whereinthe substituents on the phenyl ring are halogen, (C₁-C₈)alkoxy,(C₁-C₈)haloalkoxy, (C₁-C₈)alkylthio, hydroxyl, amino, nitro, carboxyl,cyano, azido (C₁-C₈)alkoxycarbonyl, (C₁-C₈)alkylcarbonyl, formyl,carbamoyl, mono- and di -(C₁-C₈) alkylaminocarbonyl, acylamino, mono-and di-(C₁-C₈) alkylamino, (C₁-C₈)alkylsulfinyl,(C₁-C₈)haloalkylsulfinyl, (C₁-C₈)alkylsulfonyl,halo(C₁-C₈)alkylsulfonyl, (C₁-C₈)cycloalkyl, (C₁-C₈) cycloalkenyl,wherein the cycloalkyl and cycloalkyl radicals are optionallysubstituted by (C₁-C₈)alkyl and halo(C₁-C₈)alkyl, (C₁-C₈)alkenyl,(C₁-C₈)alkynyl, (C₁-C₈)alkenyloxy or (C₁-C₈)alkynyloxy.
 6. A process forthe preparation of a compound of the formula (XIII) as defined in claim5,

comprising steps B) and C1) or B), C2.1) and C2.2) as defined in claim5.
 7. A process for the preparation of a compound of the formula (VII)as defined in claim 5,

wherein a compound of the formula (I) as defined in claim 1 and in whichR², R³═H is diazotized in the presence of an acid and subsequentlyreacted with an SO₂ source in the presence of a copper catalyst and anacid.
 8. A process for the preparation of a compound of the formula(VIII) as defined in claim 5,

comprising the steps of A) reacting a compound of the formula (I) asdefined in claim 1 and in which R², R³═H to give a compound of theformula (VII),

wherein the compound of the formula (I) is diazotized in the presence ofan acid and subsequently reacted with an SO₂ source in the presence of acopper catalyst and of an acid, and subsequently B) reacting thecompound of the formula (VII) to give a compound of the formula (VIII),

wherein the compound of the formula (VIII) is subjected to aminolysis ina suitable solvent with ammonia.
 9. A compound of the formula (Z′) or(Za′)

in which R¹ is H, (C₁-C₈)alkyl, (C₃-C₈)alkenyl or (C₃-C₈)alkynyl, wherethe last 3 radicals are unsubstituted or substituted, R⁸ radicals areidentical or different and are (C₁-C₄)alkyl, (C₁-C₄)alkoxy,[(C₁-C₄)alkyl]carbonyl or [(C₁-C₄)alkyl]carbonyl which are unsubstitutedor substituted, or R⁸ is halogen, NO₂ or CN, n is 0, 1, 2 or 3, X⁻ is anequivalent of an acid anion Z is NH₂ or NO₂ and R¹ is not H if Z is NO₂wherein, unless otherwise identified, the substituents are halogen,(C₁-C₈)alkoxy, (C₁-C₈)haloalkoxy, (C₁-C₈)alkylthio, hydroxyl, amino,nitro, carboxyl, cyano, azido (C₁-C₈)alkoxycarbonyl,(C₁-C₈)alkylcarbonyl, formyl, carbamoyl, mono- anddi-(C₁-C₈)dialkylaminocarbonyl, acylamino, mono- and di-(C₁-C₈)alkylamino, (C₁-C₈)alkylsulfinyl, (C₁-C₈)haloalkylsulfinyl,(C₁-C₈)alkylsulfonyl, halo(C₁-C₈)alkylsulfonyl, (C₁-C₈)cycloalkyl,(C₁-C₈) cycloalkenyl, wherein the cycloalkyl and cycloalkyl radicals areoptionally substituted by (C₁-C₈)alkyl and halo(C₁-C₈)alkyl,(C₁-C₈)alkenyl, (C₁-C₈)alkynyl, (C₁-C₈)alkenyloxy or (C₁-C₈)alkynyloxy.